Materials Research.

2014; 17(1): 83-87 © 2014

DDOI: http://dx.doi.org/10.1590/S1516-14392013005000153

A Systematic Study on Electrolytic Production of Hydrogen

Gas by Using Graphite as Electrode

A.L. Yuvaraja, D. Santhanarajb*

Department of Mechanical Engineering, Veltech high tech DR.RR and DR. SR Engineering college,
a

Avadi, Chennai 600 062, Índia

b
Department of Chemistry, Veltech high tech DR.RR and DR. SR Engineering college, Avadi,
Chennai 600 062, Índia

Received: December 4, 2012; Revised: August 26, 2013

Alkaline water electrolysis is one of the easiest methods for hydrogen production that has
the advantage of simplicity. The major challenges in the water electrolysis are the reduce energy
consumption, cost and maintenance and to increase reliability, durability and safety. In this regard,
the electrolytic production of hydrogen is systematically studied by commercially available graphite
electrode at room temperature. The experimental results showed the rate of production of hydrogen
gas was significantly affected when the reaction parameters such as effect of electrolyte concentration,
temperature, applied voltage and reaction time are varied. From the experimental results, it has been
found that graphite is a good choice for the production of maximum hydrogen compared to various
other electrodes.

Keywords: electrochemistry, electrolyte, gas bubbles, hydrogen, renewable energy, water

electrolysis

1. Introduction
Hydrogen plays an important role as an energy carrier reaction by accumulating or consuming materials of
for sustainable development1-8 and it is also expected to be electrodes.
used as secondary energy in near feature. Hydrogen can Steel and iron are the most commonly used for
also be used as fuel for vehicle and rockets, as chemical, for electrolysis of water. These electrodes are used as anode
Ni-H2 electric cell, for direct combustion for heat, and so and it is sacrificed in electrolysis, as the anode rusts
on. Besides, hydrogen is considered as the lightest element (get oxidized) and the cathode de-rusts (get reduced). Many
and any leakage of hydrogen gas can be dispersed quickly. works have been carried out in stainless steel, brass and
Thus, hydrogen is believed as safe as other commonly used aluminum as anodes, due to the familiar corrosion-resistant
fuels for future10. Presently, hydrogen can be economically properties of these materials. Unfortunately, stainless steel
produced from hydrocarbon reforming, which is neither releases toxic materials when it decays, brass deposits
renewable nor clean from the life cycle point of view9-11. copper onto the cathode (which accelerates rusting of steel),
Powered by solar energy, hydrogen can be produced from and aluminum quickly deteriorates. In this connection,
water via photocatalysis, thermochemical cycles, and water the carbon based electrodes such as carbon and graphite
electrolysis10-13. These methods offer renewable and clean are much more interested due to low cost, good electrical
production of hydrogen fuel and therefore, have attracted and thermal conductivity, the relatively inert property
increasing research interests in recent years. So far, the in alkaline solution compared to metals and also for its
efficiency of photocatalysis and thermochemical cycles are porous structure with high purity. The porous structure
still too low to be economically competitive. Electrolytic helps graphite to adsorb hydrogen molecules15. However,
production of hydrogen from water is gradually gaining the hydrogen production is not systematically studied over
its importance among the other conventional processes of the graphite electrode to improve hydrogen production by
hydrogen production in the context of renewable energy simple electrolytic process. In the present paper, the effects
source utilization and environmentally clean technology. of electrolyte concentration, temperature, applied voltage
Worldwide research is being carried out to make the process and reaction time on the amount of hydrogen gas produced
into cost effective. and consequently on the overall electrolysis efficiency is
An electrolyzer is usually subject to massive current experimentally investigated.
values in order to break the water molecules into oxygen
and hydrogen. In any electrolytic cell, electrodes are the 2. Experimental
main physical part of the system14. Out of the two types
The experiment is carried out as in the setup shown in
of electrodes, active electrodes get involved in the redox
Figure 1. It consists of two compartments (ID and height of
*e-mail: [email protected] each compartment were 6 cm and 20 cm, respectively) in the
84 Yuvaraj & Santhanaraj Materials Research

electrolyzer of total capacity of 1.5 liter. They are connected

by a narrow rectangular conduit of size (15 cm × 4.5 cm ×
4 cm). Cylindrical rods namely 316 L stainless steel, EN8,
Carbon and graphite electrodes are used with uniform
dimensions (diameter = 20 mm & length = 80 mm) and
alkaline KOH was used as standard electrolytes. The
distance between the two electrodes is kept constant at a
value of 2 cm. AC power supply is connected to a bridge
rectifier through a step down transformer (500 VA, Input:
0 - 220/ 230 V AC, Output: 0 - 24 V AC). The electrodes are
then connected with bridge rectifier (AC to DC converter).
The range of DC output is varied from 0 to 12 V. A variac
is used to vary the applied voltage. Ammeter (0 - 20 A DC)
and voltmeter (0 - 50 V DC) are connected respectively in Figure 1. A schematic diagram represents the electrolytic
series and parallel to the electrolyzer to measure current and production of hydrogen gas.
voltage applied to the system. The gases obtained from the
anode and the cathode limbs are collected separately. The
volume of hydrogen produced is twice the amount of oxygen
produced and it can be measured by down displacement
method.

3. Results and Discussions

3.1. Effect of electrolyte concentration

Bases and acids are known to change the nonconductive
nature of pure water. These compounds have a great
reducing effect on the overvoltage value of an electrolyzer16.
They improve the ionic conductivity aqueous electrolyte
compounds. However, the concentration level of acidic
and alkali solutions are limited in practice due to the
highly corrosive behavior of electrodes. In this regard, the
concentration of electrolyte was systematically varied from Figure 2. Effect of electrolyte concentration on the production of
0.05 to 0.4 M concentration as shown in Figure 2. The study hydrogen gas: Reaction conditions: Dimensional of graphite rod:
revealed that the hydrogen production gradually increases 80 × 20mm; Temperature: 303 K; Pressure: 1 atm; Applied voltage:
12 V; Applied Current: 1.2 A; Reaction Time: 10 mts and Distance
with increase in electrolytic concentration. This may be
between the electrodes: 2 cm.
due to the amount of current that passes depends on the
conductance of the electrodes and electrolyte concentration.
In another perspective, the increase in hydrogen evolution
in increased electrolytic concentration is due to a greater
number of effective ionic collisions per unit time.

3.2. Effect of decomposition of graphite

electrodes (Anodic reaction)
The effect of various electrolytic concentrations on
graphite electrodes is studied and represented in Figure 3.
The results are shown that when there is an increase in
electrolytic concentration from 0.025 to 0.5 M, the gradual
decomposition of anodic graphite rod is observed. The
decomposition behavior of graphite rod is calculated by
weight loss after the electrolytic process. The weight loss
may be due to high electrolytic concentration in the presence
of applied voltage. The KOH acts up to the surface carbon
of graphite material and it leads to the electrolytic solution Figure 3. Effect of Weight Loss on Graphite Rod with respect
to electrolyte concentration: Reaction conditions: Dimensional
turning into black slurry. From the results, we concluded
of graphite rod: 80 × 20mm; Temperature: 303 K; Pressure: 1
that the high electrolytic concentration (above 0.025 M) is atm; Applied voltage: 12 V; Applied Current: 1.2 A; Medium:
not beneficial for long time hydrogen production without Distilled water; Reaction Time: 10 mts and Distance between the
destruction of graphite electrode. electrodes: 2 cm.
2014; 17(1) A Systematic Study on Electrolytic Production of Hydrogen Gas by Using Graphite as Electrode 85

3.3. Effect of temperature From the linear graph, the resistivity of aqueous KOH is
calculated as 19.5 ohms.
Temperature is known to be one of the most effective
variables on the electric power demand of an electrolytic 3.5. Effect of applied voltage
cell. Electrolysis process is much more efficient at increased
The influence of an applied voltage on the hydrogen
temperatures17. In this part of the experiment, the electrolyte
evolution reaction (HER) can be studied over cylindrical
temperature has gradually increased from 270 to 353 K
graphite electrode at the temperature of 593 K with a
(Figure 4). The study clearly reveals that when there is an
0.025 M concentration of KOH. The applied voltage is
increase in temperature the hydrogen production increases
varied from 4.5 to 12 V and the resultant graph as shown in
linearly. The reasons for this behavior can be drawn from
Figure 6. It shows that, the rate of production of hydrogen
the thermodynamic characteristics of a water molecule gas gradually increases with increase in applied voltage. The
since its splitting reaction potential is known to reduce as plausible reason is the uniform charge density increases on
the temperature increases. Moreover, ionic conductivity the surface of cylindrical electrode.
and surface reaction of an electrolyte rise directly with
temperature18. High temperature water electrolysis requires 3.6. Effect of time on stream
less energy to reach any given current density in analogy In order to study the sustainability and stability of the
with a low temperature process18,19. The main outcome of the cylindrical graphite electrode, the effect of time on the
study is that a substantial part of the energy needed for the hydrogen evolution reaction is studied under the optimized
electrolysis process is added as heat, which is much cheaper reaction conditions. The obtained results were illustrated
than electric energy. In addition, the high temperature in Figure 7. From the figure, it was observed that initially
accelerates the reaction kinetics, reducing the energy loss the hydrogen production was reached to maximum of
due to electrode polarization, thus increasing the overall 800 cc/min and thereby decreased to attain the stable state.
system efficiency. The unchanged profile of hydrogen production for the period
of 90 minutes demonstrates that the graphite electrode
3.4. Ohmic losses
remains stable state without any destruction on the surface of
The ohmic losses are due to the resistance of the the electrode throughout the testing time. After the reaction
imperfect electrodes and the nature electrolytes. The time of 90 minutes, the graphite electrode is regenerated by
resistivity of the given electrolytic solution can be drying in flow of air at 50 °C for five hours and the experiment
calculated by varying the current density with respect to is conducted under similar reaction conditions. The rate of
applied voltage as shown in Figure 5. It is clearly shows production of hydrogen is much more similar to that of initial
that, the ohmic loss of the alkaline KOH is perfectly run. This means the graphite electrode regain its original
linear20. In most cases, the ohmic loss is considered to have activity of its regeneration. The overall performance of the
the relationship of I (Current) and R, where R is constant. graphite electrode has shown an acceptable level of stability
So, the equation  is related to the ohmic loss is V  =  IR. under the present experimental conditions.

Figure 4. Effect of temperature on the production of hydrogen

gas: Dimensional of graphite rod: 80 × 20mm; Pressure: 1 atm; Figure 5. Effect of applied voltage on the production of hydrogen
Electrolyte concentration: 0.03 M; Applied voltage: 12 V; Applied gas: Dimensional of graphite rod: 80 × 20mm; Temperature: 303 K;
Current: 1.2 A; Medium: Distilled water; Reaction Time: 10 mts Pressure: 1 atm; Electrolyte concentration: 0.03 M; Reaction Time:
and Distance between the electrodes: 2 cm. 10 mts and Distance between the electrodes: 2 cm.
86 Yuvaraj & Santhanaraj Materials Research

Figure 8. Influence of various cylindrical electrodes on the

Figure 6. Effect of time on stream on the production of hydrogen production of hydrogen gas: Dimensional of graphite rod:
gas: Dimensional of graphite rod: 80 × 20mm; Temperature: 303 K; 80 × 20mm; Temperature: 303 K; Pressure: 1 atm; Electrolyte
Pressure: 1 atm; Electrolyte concentration: 0.03 M; Applied voltage: concentration: 0.03 M; Applied voltage: 12 V; Applied Current:
12 V; Applied Current: 1.2 A; Distance between the electrodes: 2 cm. 1.2 A; Distance between the electrodes: 2 cm.

layer of structure graphite electrode or the porous nature

of material which significantly enhances the diffusion of
water molecule without any blockage. On the other hand, the
contact time of water molecule per unit time is much higher
on graphite electrode than the carbon electrode. Therefore,
from the above results it might be concluded that hydrogen
evolution reaction is preferentially taking place in the internal
porous structure. Further, the significant corrosion behavior
can be seen on both stainless steel and EN8 electrodes by
using alkaline KOH as the electrolyte and it leads to decrease
in the rate of hydrogen production. The observed trend is
more pronounced on EN8 electrode compared to the stainless
steel electrode. Among all the cylindrical electrodes, graphite
is found to be the best choice for hydrogen evolution reaction
under the present experimental conditions.

3.8. Kinetic studies on electrolysis of water

The rate data for the alkaline water electrolysis is studied
Figure 7. Arrhenius plots for the production of hydrogen gas: on cylindrical graphite electrode and it could be fitted well
Dimensional of graphite rod: 80 × 20mm; Pressure: 1 atm; to first order rate law. The following relationship derived
Electrolyte: KOH; Electrolyte concentration: 0.03 M; Applied between relative conversion ‘X’ and contact time has been
voltage: 12 V; Applied Current: 1.2 A; Distance between the used for evaluating the rate parameters.
electrodes: 2 cm.
kt = -ln (1-X) (1)
Where, ‘X’ is the fractional conversion of hydrogen gas,
3.7. Effect of electrodes on the hydrogen ‘k’ is the apparent first order rate constant. From the slope
evolution reaction of linear plot, the first order rate constant value ‘k’ can be
calculated by using equation 1, which is used to determine
The efficiency of graphite electrode is compared with
the activity of electrodes through the evaluation of activation
commercially available various electrodes like 316 L stainless
energy. The apparent activation energy is calculated as
steel, EN8 and carbon rods and the results are shown in
7.5 cal/mol.
Figure 8. The activity of various electrodes follows the trend
Graphite > EN8 > SS 316 L > Carbon. From the experimental
results, it was observed that even though, the carbon and 4. Conclusions
graphite electrodes are allotropy of carbon materials, the The Electrolytic production of hydrogen is systematically
efficiency of hydrogen production is much higher on graphite studied by using commercially available graphite electrode
electrode. The plausible reasons it may be due to the either at room temperature. On increasing the electrolytic
2014; 17(1) A Systematic Study on Electrolytic Production of Hydrogen Gas by Using Graphite as Electrode 87

concentration the hydrogen production is greatly increases. various electrodes like 316 L stainless steel, EN8 and carbon
However, the gradual decomposition of anodic graphite rods rods. Among all the cylindrical electrodes, graphite is found
is observed. From the study we concluded that the high to be the best choice for hydrogen evolution reaction under
electrolytic concentration (above 0.025 M) is not beneficial the present experimental conditions. Further research is
for long time hydrogen production. The efficiency of necessary to develop this laboratory scale study into a
graphite electrode is compared with commercially available practical reality.

References 11. Koroneos C, Dompros A, Roumbas G and Moussiopoulos N.

Life cycle assessment of hydrogen fuel production processes.
1. Silva LD, Bergel A, Feron D and Basseguy R. Hydrogen International Journal of Hydrogen Energy. 2004; 29:1443‑1450.
production by electrolysis of a phosphate solution on a http://dx.doi.org/10.1016/j.ijhydene.2004.01.016
stainless steel cathode. International of Journal of Hydrogen
12. Nie J, Chen Y, Boehm RF and Katukota S. A Photoelectrochemical
Energy. 2010; 35:8561-8568. http://dx.doi.org/10.1016/j.
Model of Proton Exchange Water Electrolysis for Hydrogen
ijhydene.2010.05.101 Production. Journal of Heat Transfer. 2008; 130:042409-
2. Zeng K and Zhang D. Recent progress in alkaline water 042415. http://dx.doi.org/10.1115/1.2789722
electrolysis for hydrogen production and applications. Progress 13. Colella WG, Jcobson MZ and Golden DM. Switching to a
in Energy and Combust Science. 2010; 36:307-326. http:// U.S. hydrogen fuel cell vehicle fleet: The resultant change
dx.doi.org/10.1016/j.pecs.2009.11.002 in emissions, energy use, and greenhouse gases. Journal of
3. Wei G, Wang Y, Huang C, Zhitao QG and Xu L. The stability Power Sources. 2005;150:150-181. http://dx.doi.org/10.1016/j.
of MEA in SPE water electrolysis for hydrogen production. jpowsour.2005.05.092
International Journal of Hydrogen Energy. 2010; 35:3951‑3957. 14. Allouche A, Ferro Y, Angot T, Thomas C and Layet JM.
http://dx.doi.org/10.1016/j.ijhydene.2010.01.153 Hydrogen adsorption on graphite (0001) surface: A combined
4. Ni M, Leung MKH, Sumathy K and Leung DYC. spectroscopy–density-functional-theory study. Journal of
Potential of renewable hydrogen production for energy Chemical Physics. 2005; 123:124701-6. PMid:16397948.
supply in Hong Kong. International Journal of Hydrogen http://dx.doi.org/10.1063/1.2043008
Energy. 2006; 31:1401‑1412. http://dx.doi.org/10.1016/j. 15. Millet P, Andolfatto F and Durand R. Design and performance
ijhydene.2005.11.005 of a solid polymer electrolyte water electrolyzer. International
5. Rachid M and Sofiane M. Electrolyte process of hydrogen Journal of Hydrogen Energy. 1996; 21:87-93. http://dx.doi.
production by solar energy. Desalination. 2007; 206:69-77. org/10.1016/0360-3199(95)00005-4
http://dx.doi.org/10.1016/j.desal.2006.04.050 16. Badwal SPS, Giddey S and Ciacchi FT. Hydrogen and oxygen
6. Elias DC, Nair RR, Mohiuddin TMG, Morozov SV, generation with polymer electrolyte membrane (PEM)-based
electrolytic technology Ionics. 2006; 12:7-14. http://dx.doi.
Blake P, Halsall MP et al Control of graphene’s properties
org/10.1007/s11581-006-0002-x
by reversible hydrogenation: Evidence for graphane.
Science. 2009; 323: 610-613. PMid:19179524. http://dx.doi. 17. Nikolic VM, Tasic GS, Maksic AD, Saponjic DP, Miulovic
org/10.1126/science.1167130 SM and Marceta Kaninski MP. Performance comparison
of modified poly(vinyl alcohol) based membranes in
7. Politano A and Chiarello G. Alkali-induced hydrogenation
alkaline fuel cells. International Journal of Hydrogen
of epitaxial graphene by water splitting at 100 K. Journal of Energy. 1996; 36:11004-11010. http://dx.doi.org/10.1016/j.
Chemical Physics. 2013; 138: 044703. PMid:23387611. http:// ijhydene.2011.05.164
dx.doi.org/10.1063/1.4788619
18. Udagawa J, Aguiar P and Brandon NP. Hydrogen
8. Politano A, Raimondo Marino A, Formoso A and Chiarello G. production through steam electrolysis: Model-based steady
Hydrogen bonding at the water/quasi-freestanding graphene state performance of a cathode-supported intermediate
interface. Carbon. 2011; 49: 5180-5184. http://dx.doi. temperature solid oxide electrolysis cell. Journal of Power
org/10.1016/j.carbon.2011.07.034 Sources.  2007; 166:127-136. http://dx.doi.org/10.1016/j.
9. Chen F, Liu J, Chen H and Yan C. Study on Hydrogen Evolution jpowsour.2006.12.081
Reaction at a Graphite Electrode in the All-Vanadium Redox 19. Stojic DL, Marceta MP, Sovilj SP and Miljanic SS. A
Flow Battery. International Journal of Electrochemical Photoelectrochemical Model of Proton Exchange Water
Science. 2012; 7:3750-3764. Electrolysis for Hydrogen Production. Journal of Power
10. Schulte I, Hart D and Van der Vorst R. Issues affecting the Sources. 2003; 118:315-319.
acceptance of hydrogen fuel. International Journal of Hydrogen 20. Bockris JOM, Conway BE, Yeager E and White RE.
Energy 2004; 29:677-685. http://dx.doi.org/10.1016/j. Comprehensive Treatise of Electrochemistry. New York:
ijhydene.2003.09.006 Plenum Press; 1981.